Design of LPSO Phases in Mg-Y-Ni Alloys to Impact Hydrogenation Kinetics

Hydrogen Pub Date : 2023-09-10 DOI:10.3390/hydrogen4030042
Kyle S. Nicholson, Vladimir Skripnyuk, Chunjie Xu, Xiang Gao, Eugen Rabkin, Peter D. Hodgson, Rimma Lapovok
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Abstract

A series of Mg-Y-Ni alloys with different volume fractions of long-period stacking-ordered (LPSO) phase were prepared, by controlling the alloy composition, heat treatment, and single-pass extrusion, to assess the influence of increasing LPSO phase volume fraction on the hydrogen absorption and desorption properties of the extruded alloys. The LPSO phase volume fraction in the alloys increased with increasing solute concentration, from ~24% LPSO in Mg97Y2Ni1 (at.%) to ~60% LPSO in Mg93Y4Ni3 (at.%) up to ~92% LPSO in Mg91Y5Ni4 (at.%). The most refined microstructure was obtained in the alloy with highest volume fraction of LPSO phase. After 100 s at 300 °C, the Mg91Y5Ni4 alloy absorbed 4.6 ± 0.2 wt.% H while the Mg97Y2Ni1 and Mg93Y4Ni3 alloys each absorbed 3.8 ± 0.2 wt.% H. After 10,000 s at 300 °C, all three alloys had absorbed a maximum of 5.3 ± 0.2 wt.% H with no further significant difference in hydrogen absorption kinetics. The Mg91Y5Ni4 alloy desorbed 1.8 ± 0.2 wt.% H after 100 s at 300 °C against a vacuum while the Mg97Y2Ni1 and Mg93Y4Ni3 alloys desorbed 0.8 ± 0.2 wt. H and 0.6 ± 0.2 wt.% H, respectively. After 10,000 s at 300 °C, the Mg91Y5Ni4 and Mg97Y2Ni1 alloys completely desorbed 5.2 ± 0.2 wt.% H and 5.4 ± 0.2 wt.% H, respectively, but the Mg93Y4Ni3 alloy desorbed only 3.7 ± 0.2 wt.% H. Hydrogen absorption and desorption kinetics were fastest in the Mg91Y5Ni4 alloy with the highest LPSO volume fraction, but no consistent trend with LPSO phase volume fraction was observed with the Mg93Y4Ni3 alloy, which showed the slowest absorption and desorption kinetics. The hydrogen pressures corresponding to metal–hydride equilibrium did not vary with LPSO phase volume fraction or alloy composition, indicating that the (de)hydrogenation thermodynamics were not significantly changed in any of the alloys. Hydrogen absorption experiments with thin foils, made of extruded Mg91Y5Ni4 alloy with the highest LPSO phase fraction, demonstrated that the LPSO structures decompose into Mg phase, Mg2Ni phase, lamellar Mg/Mg-Y structures, and YHx particles. This study shows that hydrogen kinetics can be impacted in Mg-Y-Ni alloys by controlling the LPSO phases using common metallurgical techniques.
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影响Mg-Y-Ni合金氢化动力学的LPSO相设计
通过控制合金成分、热处理和单道次挤压,制备了一系列具有不同长周期堆积有序相体积分数的Mg-Y-Ni合金,考察了增加长周期堆积有序相体积分数对挤压合金吸氢和脱氢性能的影响。合金中LPSO相体积分数随溶质浓度的增加而增加,从Mg97Y2Ni1中的~24% (at.%)到Mg93Y4Ni3中的~60% (at.%),再到Mg91Y5Ni4中的~92% (at.%)。在LPSO相体积分数最高的合金中,组织最细化。在300℃下加热100 s后,Mg91Y5Ni4合金吸收了4.6±0.2 wt.% H,而Mg97Y2Ni1和Mg93Y4Ni3合金分别吸收了3.8±0.2 wt.% H。在300℃下加热10,000 s后,三种合金的吸氢动力学均达到了5.3±0.2 wt.% H,且吸氢动力学没有进一步的显著差异。在300℃真空条件下,Mg91Y5Ni4合金在100 s后的解吸氢量为1.8±0.2 wt.%,而Mg97Y2Ni1和Mg93Y4Ni3合金的解吸氢量分别为0.8±0.2 wt.%和0.6±0.2 wt.%。在300℃下加热10000 s后,Mg91Y5Ni4和Mg97Y2Ni1合金分别完全解吸5.2±0.2 wt.% H和5.4±0.2 wt.% H,而Mg93Y4Ni3合金仅解吸3.7±0.2 wt.% H。氢的吸附和解吸动力学在LPSO体积分数最高的Mg91Y5Ni4合金中最快,而在LPSO相体积分数最高的Mg93Y4Ni3合金中没有一致的趋势,其吸附和解吸动力学最慢。金属氢化物平衡对应的氢压力不随LPSO相体积分数或合金成分的变化而变化,表明合金的(脱)氢化热力学没有明显变化。用LPSO相分数最高的Mg91Y5Ni4挤压合金薄片进行吸氢实验,发现LPSO结构分解为Mg相、Mg2Ni相、层状Mg/Mg- y结构和YHx颗粒。本研究表明,使用常规冶金技术控制LPSO相可以影响Mg-Y-Ni合金中的氢动力学。
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